Stiff and self-healing hydrogels by polymer entanglements in co-planar nanoconfinement
Source abstract
Abstract
Abstract Many biological tissues are mechanically strong and stiff but can still heal from damage. By contrast, synthetic hydrogels have not shown comparable combinations of properties, as current stiffening approaches inevitably suppress the required chain/bond dynamics for self-healing. Here we show a stiff and self-healing hydrogel with a modulus of 50 MPa and tensile strength up to 4.2 MPa by polymer entanglements in co-planar nanoconfinement. This is realized by polymerizing a highly concentrated monomer solution within a scaffold of fully delaminated synthetic hectorite nanosheets, shear oriented into a macroscopic monodomain. The resultant physical gels show self-healing efficiency up to 100% despite the high modulus, and high adhesion shear strength on a broad range of substrates. This nanoconfinement approach allows the incorporation of novel functionalities by embedding colloidal materials such as MXenes and can be generalized to other polymers and solvents to fabricate stiff and self-healing gels for soft robotics, additive manufacturing and biomedical applications.
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Research context
OpenAlex topics: Hydrogels: synthesis, properties, applications · Advanced Materials and Mechanics · Advanced Sensor and Energy Harvesting Materials
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References (58)
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1. Chen, J. H., Liu, C., You, L. & Simmons, C. A. Boning up on Wolff’s law: mechanical regulation of the cells that make and maintain bone. J. Biomech. 43, 108–118 (2010).10.1016/j.jbiomech.2009.09.016 ↗
2. Schoenfeld, B. J. The mechanisms of muscle hypertrophy and their application to resistance training. J. Strength Cond. Res. 24, 2857–72 (2010).10.1519/JSC.0b013e3181e840f3 ↗
3. Liu, Y. et al. Soft and elastic hydrogel-based microelectronics for localized low-voltage neuromodulation. Nat. Biomed. Eng. 3, 58–68 (2019).10.1038/s41551-018-0335-6 ↗
4. Zhou, T. et al. 3D printable high-performance conducting polymer hydrogel for all-hydrogel bioelectronic interfaces. Nat. Mater. 22, 895–902 (2023).10.1038/s41563-023-01569-2 ↗
5. Yuk, H., Wu, J. & Zhao, X. Hydrogel interfaces for merging humans and machines. Nat. Rev. Mater. 7, 935–952 (2022).10.1038/s41578-022-00483-4 ↗
6. Matsuda, T., Kawakami, R., Namba, R., Nakajima, T. & Gong, J. P. Mechanoresponsive self-growing hydrogels inspired by muscle training. Science 363, 504–508 (2019).10.1126/science.aau9533 ↗
7. Hua, M. et al. Strong tough hydrogels via the synergy of freeze-casting and salting out. Nature 590, 594–599 (2021).10.1038/s41586-021-03212-z ↗
8. Lin, W. et al. Cartilage-inspired, lipid-based boundary-lubricated hydrogels. Science 370, 335–338 (2020).10.1126/science.aay8276 ↗
9. Jian, N. et al. Bioinspired self‐growing hydrogels by harnessing interfacial polymerization. Adv. Mater. 35, 2210609 (2023).10.1002/adma.202210609 ↗
10. Taylor, D. L. & in het Panhuis, M. Self‐healing hydrogels. Adv. Mater. 28, 9060–9093 (2016).10.1002/adma.201601613 ↗
11. Wang, S. & Urban, M. W. Self-healing polymers. Nat. Rev. Mater. 5, 562–583 (2020).10.1038/s41578-020-0202-4 ↗
12. Wang, M. et al. Tough and stretchable ionogels by in situ phase separation. Nat. Mater. 21, 359–365 (2022).10.1038/s41563-022-01195-4 ↗
13. Caprioli, M. et al. 3D-printed self-healing hydrogels via digital light processing. Nat. Commun. 12, 2462 (2021).10.1038/s41467-021-22802-z ↗
14. Fang, X. et al. Dynamic hydrophobic domains enable the fabrication of mechanically robust and highly elastic poly(vinyl alcohol)-based hydrogels with excellent self-healing ability. ACS Mater. Lett. 2, 764–770 (2020).10.1021/acsmaterialslett.0c00075 ↗
15. Haraguchi, K., Uyama, K. & Tanimoto, H. Self-healing in nanocomposite hydrogels. Macromol. Rapid Commun. 32, 1253–1258 (2011).10.1002/marc.201100248 ↗
16. Wang, Z. et al. A rapidly self-healing host-guest supramolecular hydrogel with high mechanical strength and excellent biocompatibility. Angew. Chem. Int. Ed. 57, 9008–9012 (2018).10.1002/anie.201804400 ↗
17. Sun, T. L. et al. Physical hydrogels composed of polyampholytes demonstrate high toughness and viscoelasticity. Nat. Mater. 12, 932–937 (2013).10.1038/nmat3713 ↗
18. Luo, F. et al. Oppositely charged polyelectrolytes form tough, self-healing, and rebuildable hydrogels. Adv. Mater. 27, 2722–2727 (2015).10.1002/adma.201500140 ↗
19. Qin, H. et al. Dynamic Au-thiolate interaction induced rapid self-healing nanocomposite hydrogels with remarkable mechanical behaviors. Chem 3, 691–705 (2017).10.1016/j.chempr.2017.07.017 ↗
20. Zhang, H. J. et al. Tough physical double-network hydrogels based on amphiphilic triblock copolymers. Adv. Mater. 28, 4884–4890 (2016).10.1002/adma.201600466 ↗
21. Jiang, Z., Diggle, B., Shackleford, I. C. G. & Connal, L. A. Tough, self-healing hydrogels capable of ultrafast shape changing. Adv. Mater. 31, 1904956 (2019).10.1002/adma.201904956 ↗
22. Jiang, Z. et al. Strong, self-healable, and recyclable visible-light-responsive hydrogel actuators. Angew. Chem. Int. Ed. 59, 7049–7056 (2020).10.1002/anie.201916058 ↗
23. Zheng, S. Y. et al. Metal-coordination complexes mediated physical hydrogels with high toughness, stick–slip tearing behavior, and good processability. Macromolecules 49, 9637–9646 (2016).10.1021/acs.macromol.6b02150 ↗
24. Mredha, Md. T. I. et al. A facile method to fabricate anisotropic hydrogels with perfectly aligned hierarchical fibrous structures. Adv. Mater. 30, 1704937 (2018).10.1002/adma.201704937 ↗
25. Wang, Y. J. et al. Ultrastiff and tough supramolecular hydrogels with a dense and robust hydrogen bond network. Chem. Mater. 31, 1430–1440 (2019).10.1021/acs.chemmater.8b05262 ↗
26. Rauner, N., Meuris, M., Zoric, M. & Tiller, J. C. Enzymatic mineralization generates ultrastiff and tough hydrogels with tunable mechanics. Nature 543, 407–410 (2017).10.1038/nature21392 ↗
27. Ní Annaidh, A., Bruyère, K., Destrade, M., Gilchrist, M. D. & Otténio, M. Characterization of the anisotropic mechanical properties of excised human skin. J. Mech. Behav. Biomed. Mater. 5, 139–148 (2012).10.1016/j.jmbbm.2011.08.016 ↗
28. Grommet, A. B., Feller, M. & Klajn, R. Chemical reactivity under nanoconfinement. Nat. Nanotechnol. 15, 256–271 (2020).10.1038/s41565-020-0652-2 ↗
29. Ellison, C. J. & Torkelson, J. M. The distribution of glass-transition temperatures in nanoscopically confined glass formers. Nat. Mater. 2, 695–700 (2003).10.1038/nmat980 ↗
30. Xue, Y. et al. Atomic-scale ion transistor with ultrahigh diffusivity. Science 372, 501–503 (2021).10.1126/science.abb5144 ↗
31. Xu, J. et al. Highly stretchable polymer semiconductor films through the nanoconfinement effect. Science 355, 59–64 (2017).10.1126/science.aah4496 ↗
32. Liu, L. et al. Dynamic nanoconfinement enabled highly stretchable and supratough polymeric materials with desirable healability and biocompatibility. Adv. Mater. 33, 2105829 (2021).10.1002/adma.202105829 ↗
33. Li, W. et al. Nanoconfined polymerization limits crack propagation in hysteresis-free gels. Nat. Mater. 23, 131–138 (2023).10.1038/s41563-023-01697-9 ↗
34. Park, J. et al. Intrinsically nonswellable multifunctional hydrogel with dynamic nanoconfinement networks for robust tissue‐adaptable bioelectronics. Adv. Sci. 10, 2207237 (2023).10.1002/advs.202207237 ↗
35. O’Connell, P. A. & McKenna, G. B. Rheological measurements of the thermoviscoelastic response of ultrathin polymer films. Science 307, 1760–1763 (2005).10.1126/science.1105658 ↗
36. Lake, G. J. & Thomas, A. G. The strength of highly elastic materials. Proc. R. Soc. Lond. A 300, 108–119 (1967).10.1098/rspa.1967.0160 ↗
37. Kim, J., Zhang, G., Shi, M. & Suo, Z. Fracture, fatigue, and friction of polymers in which entanglements greatly outnumber cross-links. Science 374, 212–216 (2021).10.1126/science.abg6320 ↗
38. Stöter, M. et al. Nanoplatelets of sodium hectorite showing aspect ratios of ≈20,000 and superior purity. Langmuir 29, 1280–1285 (2013).10.1021/la304453h ↗
39. Dudko, V. et al. Repulsive osmotic delamination: 1D dissolution of 2D materials. Adv. Mater. Technol. 8, 2200553 (2023).10.1002/admt.202200553 ↗
40. Rosenfeldt, S. et al. In-depth insights into the key steps of delamination of charged 2D nanomaterials. Langmuir 32, 10582–10588 (2016).10.1021/acs.langmuir.6b02206 ↗
41. Liu, M. et al. An anisotropic hydrogel with electrostatic repulsion between cofacially aligned nanosheets. Nature 517, 68–72 (2015).10.1038/nature14060 ↗
42. Zhu, Q. L. et al. Distributed electric field induces orientations of nanosheets to prepare hydrogels with elaborate ordered structures and programmed deformations. Adv. Mater. 32, 2005567 (2020).10.1002/adma.202005567 ↗
43. Wang, Q. et al. High-water-content mouldable hydrogels by mixing clay and a dendritic molecular binder. Nature 463, 339–343 (2010).10.1038/nature08693 ↗
44. Loch, P. et al. Nematic suspension of a microporous layered silicate obtained by forceless spontaneous delamination via repulsive osmotic swelling for casting high-barrier all-inorganic films. Sci. Adv. 8, eabn9084 (2022).10.1126/sciadv.abn9084 ↗
45. Yin, Z., Hannard, F. & Barthelat, F. Impact-resistant nacre-like transparent materials. Science 364, 1260–1263 (2019).10.1126/science.aaw8988 ↗
46. Zhao, C. et al. Layered nanocomposites by shear-flow-induced alignment of nanosheets. Nature 580, 210–215 (2020).10.1038/s41586-020-2161-8 ↗
47. Tang, Z., Kotov, N. A., Magonov, S. & Ozturk, B. Nanostructured artificial nacre. Nat. Mater. 2, 413–418 (2003).10.1038/nmat906 ↗
48. François, J., Sarazin, D., Schwartz, T. & Weill, G. Polyacrylamide in water: molecular weight dependence of 〈R2〉 and [η] and the problem of the excluded volume exponent. Polymer 20, 969–975 (1979).10.1016/0032-3861(79)90194-0 ↗
49. Affdl, J. C. H. & Kardos, J. L. The Halpin‐Tsai equations: a review. Polym. Eng. Sci. 16, 344–352 (1976).10.1002/pen.760160512 ↗
50. Ilyas, M. et al. Water-triggered ductile–brittle transition of anisotropic lamellar hydrogels and effect of confinement on polymer dynamics. Macromolecules 50, 8169–8177 (2017).10.1021/acs.macromol.7b01438 ↗
51. Kamiyama, Y. et al. Highly stretchable and self-healable polymer gels from physical entanglements of ultrahigh–molecular weight polymers. Sci. Adv. 8, eadd0226 (2022).10.1126/sciadv.add0226 ↗
52. Abdullah, T. & Okay, O. 4D printing of body temperature-responsive hydrogels based on poly(acrylic acid) with shape-memory and self-healing abilities. ACS Appl. Bio Mater. 6, 703–711 (2023).10.1021/acsabm.2c00939 ↗
53. Zhang, W. et al. Catechol-functionalized hydrogels: biomimetic design, adhesion mechanism, and biomedical applications. Chem. Soc. Rev. 49, 433–464 (2020).10.1039/C9CS00285E ↗
54. Yang, J., Bai, R., Chen, B. & Suo, Z. Hydrogel adhesion: a supramolecular synergy of chemistry, topology, and mechanics. Adv. Funct. Mater. 30, 1901693 (2020).10.1002/adfm.201901693 ↗
55. VahidMohammadi, A., Rosen, J. & Gogotsi, Y. The world of two-dimensional carbides and nitrides (MXenes). Science 372, eabf1581 (2021).10.1126/science.abf1581 ↗
56. Breu, J., Seidl, W., Stoll, A. J., Lange, K. G. & Probst, T. U. Charge homogeneity in synthetic fluorohectorite. Chem. Mater. 13, 4213–4220 (2001).10.1021/cm011014m ↗
57. Alhabeb, M. et al. Guidelines for synthesis and processing of two-dimensional titanium carbide (Ti3C2Tx MXene). Chem. Mater. 29, 7633–7644 (2017).10.1021/acs.chemmater.7b02847 ↗
58. Karobi, S. N. et al. Creep behavior and delayed fracture of tough polyampholyte hydrogels by tensile test. Macromolecules 49, 5630–5636 (2016).10.1021/acs.macromol.6b01016 ↗